Impact of irreversible sorption of phthalate acid esters on their sediment quality criteria

The equilibrium partitioning (EqP) method has been applied to establish sediment quality criteria (SQC); however, it does not consider the nonlinear irreversible sorption of many organic contaminants. In this research, the sorption and desorption of two phthalate esters (PAEs), dimethyl phthalate (DMP) and di(2-ethylhexyl) phthalate (DEHP), in four natural sediments collected from the Yangtze River and the Yellow River were studied; the impact of irreversible sorption of DMP and DEHP on SQC has been evaluated. Based on the reversible and irreversible biphasic sorption model, the values of maximum irreversible sorption capacity (q(max)(irr)) were 125.19 μg g(-1)-337.37 μg g(-1) for DMP and 515.87 μg g(-1)-591.40 μg g(-1) for DEHP. The q(max)(irr) value was positively related to the organic carbon and black carbon contents, cation exchange capacity, and surface area of the sediments. The values of the irreversible sorption coefficient K(oc)(irr) for both DEHP and DMP in the four sediments approximated to a constant of 10(6.46 ± 0.38), which was 1-2 orders of magnitude higher than their reversible sorption coefficient K(oc)(irr). The values of SQC for PAEs based on the EqP method were modified by involving the irreversible sorption. The modified SQC of DEHP could be 2 to 20 times higher than the value predicted by the EqP method, and the assessment results for DEHP contamination in the sediments with the modified SQC were more reasonable than those with the non-modified SQC. It indicated that the current SQC based on the EqP method may be unnecessarily strict for specific organic compounds and the irreversible sorption should be taken into account.     

Partitioning and sources of PAHs in wastewater receiving streams of Tianjin,China

Polycyclic aromatic hydrocarbons (PAHs) partitioning among dissolved phase, suspended particulate matter, pore water, and sediment was studied in one moderately contaminated river (Yongding New River) and two highly contaminated drainage canals (South Drainage Canal and North Drainage Canal) of Tianjin, China. PAHs concentrations in sediment (ranged from 0.2 to 195 μg/g) showed positive relations with both total organic carbon contents (ranged from 0.7% to 31.1%, dw) and black carbon contents (ranged from 0.1% to 2.1%, dw) in the sediments. Moreover, most of the measured organic carbon normalized partition coefficients of PAHs in the three streams were 0.76 to 1.54 log units higher than the predicted values. These indicated that strong and nonlinear sorption of PAHs by carbonaceous geosorbents such as black carbon (BC) existed in the streams, and BC was an important part of the carbonaceous particles controlling the partitioning of PAHs in the sediments of this study. PAH component ratio analyses suggested that PAHs in the three streams, effluent samples from wastewater treatment plants, and soil samples by the riverbank had similar main sources, which is coal/petroleum combustion. We suggested the transportation and transformation of both carbonaceous particles and PAHs during wastewater treatment process, surface runoff, etc, should be studied further in order to make decisions on PAHs controlling measures.     

Flame ionization gas chromatographic determination of phthalate esters in water, surface sediments and fish species in the Ogun river catchments, Ketu, Lagos, Nigeria

The detection and quantification of four phthalate esters??dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and diethylhexyl phthalate (DEHP)??in water, sediment, and some fish species were carried out using flame ionization gas chromatography. The samples were collected from the Ogun river catchments, Ketu, Lagos. The DMP was not detected in the water and fish samples but was detected in sediments collected from four of the six sampling sites. The concentration of DEP, DBP, and DEHP in the fish species ranged from 320.0?C810.0, 380.0?C1,080.0, and 40.0?C150.0 ??g/kg in Tilapia sp.; 310.0?C860.0, 400.0?C1,170.0, and 40.0?C110.0 ??g/kg in Chrysichthys sp.; and 320.0?C810.0, 400.0?C3,970.0, and 30.0?C300.0 ??g/kg (DEHP) in Synodontis sp., respectively. The differences in fish phthalate levels are not statistically significant at p?<?0.05, an indication that phthalate esters accumulation is not fish species dependent. The DEP, DBP, and DEHP values recorded are considerably higher than the maximum allowed concentrations for drinking water prescribed by the US Environmental Protection Agency. The phthalate pollution index and biosediment accumulation factor values were also calculated.     

化工废水中邻苯二甲酸酯的研究

对北京市五个化工厂的废水中8种邻苯二甲酸酯类环境激素进行分析和调查研究.在化工废水中普遍检出的邻苯二甲酸酯有邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二环己酯(DCHP),其中邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丙酯(DPrP)、邻苯二甲酸二戊酯(DAP)和邻苯二甲酸二正己酯(DHP)4种物质未检出.废水中DEHP和DBP的浓度均低于排放标准.     

Behavior of di(2-ethylhexyl) phthalate discharged from domestic waste water into aquatic environment

The behavior of di(2-ethylhexyl) phthalate (DEHP) discharged from domestic waste water into river water, sediment and submerged aquatic vegetation was investigated. The concentrations of DEHP were found to be between 8-25 microg L(-1) in river water, 1,000-2,000 microg kg(-1) in sediment and less than 20-2,000 microg kg(-1) in submerged aquatic vegetation. The experiments performed in laboratory were on the biodegradation of DEHP in water and sediment, and also adsorption equilibrium of DEHP between water and sediment. The results obtained from the investigations made it clear that the high enrichment of DEHP from water to sediment was caused from not only its high adsorptive potential but also slow degradation in sediment.     

垃圾渗滤液中DEHP与DBP的迁移演化规律研究

采用一维土柱下渗实验和垂向入渗模型相结合的方式,研究垃圾渗滤液中邻苯二甲酸二乙基己基酯（DEHP）和邻苯二甲酸二正丁酯（DBP）在土壤中的垂向迁移演化规律。结果表明：原状土和混有石英砂土的土柱对DBP的吸附能力均强于DEHP,而混有石英砂的土柱中DEHP、DBP均出现不同程度的穿透现象,且DEHP的穿透速度比DBP要快2倍;做或不做防渗处理,DEHP和DBP渗出量均呈前期快速增长而后期归于稳定的趋势,防渗对DBP效果较DEHP好;垂向入渗模型与一维土柱实验结果一致,该模型可用于其他区域有机污染物在土壤中垂向迁移的研究。     

Screening-Level Risk Assessment of Di(2-ethylhexyl)phthalate for Aquatic Organisms Using Monitoring Data in Japan

Screening-level ecological risk assessments of di(2-ethylhexyl)phthalate (DEHP) for aquatic organisms in Japan were conducted using estimated statistical values based on surface water and sediment monitoring data and effect threshold values based on a large aquatic toxicity database. An alternative method is proposed to handle monitoring data that contain nondetects including multiple detection limits and to determine the statistical values of DEHP concentrations in Japanese surface waters. The No-Observed-Effect-Concentration (NOEC_water) of DEHP for aquatic life of 77 μ g/L was determined giving equal importance to both physical effects probably caused by undissolved DEHP and to the intrinsic toxicity potentially caused by DEHP. The NOEC_sediment of 615,000 μg/kg was determined by the Equilibrium Partitioning (EqP) theory, conservatively assuming a threshold effect level in the water column as the water solubility of 3 μ g/L. The potential risks of DEHP in Japanese water environments were characterized simply by comparing the margin of exposure (MOE) with a specified uncertainty multiplier (UM). The MOE is expressed as the ratio of NOEC_water or NOEC_sediment to the expected environmental concentrations such as the 95th percentiles of the estimated DEHP concentration distributions for surface water or sediment. The results of risk characterization show that all MOE values calculated using the statistical values of DEHP concentrations in Japanese surface waters and sediments are above 10, indicating minimal risk. Although the DEHP concentrations of some surface water samples showed MOE values of less than 10, considering environmental chemistry such as bioavailable fractions and the form of existence of DEHP in a water environment, we conclude that the current levels of DEHP are of little concern to aquatic life in the majority of Japanese surface waters and sediments.     

Phenanthrene sorption to humic acids, humin, and black carbon in sediments from typical water systems in China

Humic acid (HA) and humin (HM) were extracted with 0.1 M NaOH and black carbon (BC) was isolated using a combustion method at 375°C from six sediments in different areas in China and their sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well with the Freundlich model. Among the SOM, HM and BC with more aromatic carbon controlled the sorption nonlinearity and capacity. Compared to HM, higher K _oc values were observed for BC due to the combustion of organic matter and native sorbates in HM. For HAs isotherms, a positive relation was observed between the K _oc values and aliphaticity or H/C ratios, but a negative relation was shown between the n values and polarity of HAs. HA, HM, and BC were responsible for 0.4–9.3%, 46–97%, and 65–96% of the total sorption, respectively, indicating the dominance of HM and BC fractions in overall sorption of Phen by the sediments.     

Removal of organic toxic chemicals using the spent mushroom compost of Ganoderma lucidum

The removal of the organic toxic chemicals di-n-butyl phthalate (DBP), di-2-ethyl hexyl phthalate (DEHP), nonylphenol (NP), and bisphenol-A (BPA) by laccase obtained from the spent mushroom compost (SMC) of the white rot fungi, Ganoderma lucidum, was investigated. The optimal conditions for the extraction of laccase from SMC required using sodium acetate buffer (pH 5.0, solid : solution ratio 1 : 5), and extraction over 3 h at 4 °C. The removal of NP was enhanced by adding CuSO(4) (1 mM), MnSO(4) (0.5 mM), tartaric acid (20 mM), 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS; 1 mM), and 1-hydroxybenzotriazole (HBT; 20 mg L(-1)), with ABTS yielding a higher NP removal efficiency than the other additives. At a concentration of 2 mg L(-1), DBP, DEHP, NP, and BPA were almost entirely removed by laccase after incubation for 1 day. The removal efficiencies, in descending order of magnitude, were DBP > BPA > NP > DEHP. We believe that these findings could provide useful information for improving the efficiency of the removal of organic toxic chemicals in the environment.     

Black carbon in urban topsoils of Xuzhou (China): environmental implication and magnetic proxy

Combustion-derived black carbon has received attention as a form of refractory organic carbon that may be preferentially preserved in soils and sediments. However, little is understood about the environmental roles of black carbon in urban soils. This investigation represented the preliminary study to characterize black carbon (BC) concentrations and enrichment ratios in Xuzhou urban roadside topsoil. Data from 21 roadside topsoil samples showed that the median of BC concentrations is 21.8 mg/g, which is significantly higher than local background value that averages 3.8 mg/g. Hierarchical clustering analysis indicated that BC in Xuzhou urban roadside soils are mainly from the traffic emissions. The marked positive correlations between BC and the concentrations of heavy metals (Pb, Cu, Zn, Mo, and Sc; Pearson correlation coefficient, 0.623, 0.809, 0.846, 0.742 and 0.831, respectively) suggested that these heavy metals are likely to be strongly retained by BC present in roadside topsoil. The significant positive correlation between BC and specific magnetic susceptibility was also observed. Thus, the simple environmental magnetic method is potentially an efficient alternative technique for assessing BC concentration in roadside topsoil.     

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant’s hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.     

Phthalates removal efficiency in different wastewater treatment technology in the Eastern Cape,South Africa

The removal capacity of different wastewater treatment plant (WWTP) technologies adopted in rural areas for phthalate was investigated in the Eastern Cape, South Africa. Wastewater samples collected from three selected WWTPs which use activated sludge (AS), trickling filter (TF), and oxidation pond (OP) technology were extracted using the solid-phase extraction method followed by gas chromatography-mass spectrometry (GC-MS) analysis. The six selected phthalate esters (PAEs) dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di(2-ethyl hexyl) phthalate (DEHP), and di-n-octyl phthalate (DOP) were detected in all the samples collected from the WWTPs. DBP was the most abundant compound in the influent, effluent, and sludge samples with a maximum detection of 2497 μgL^?1, 24.2 μgL^?1, and 1249 μg/g dW, respectively, followed by DEHP and BBP. There was a relatively high removal capacity achieved by AS in Alice, TF in Berlin, and OP in Bedford with a removal efficiency that varied between 77 and 99%, 76 and 98%, and 61 and 98%, respectively. A high significant correlation of PAE removal with total suspended solids (TSS) and turbidity suggests that the removal performance proceeded more through adsorption on settling particles and sludge than on biodegradation. However, the concentrations of PAEs detected in the final effluent and sludge samples exceeded acceptable levels allowed internationally for a safe aquatic environment. AS may have exhibited a more stable and better performance across the different seasons; however, pollution source control still deserves a special attention to prevent the risk posed by these micropollutants.     

Sorption and desorption of benzo(a)pyrene in aquatic systems

The sorptive behaviour of polycyclic aromatic hydrocarbons (PAHs) is critical to controlling their transport, fates and effects in the environment. Experiments are described which detail the behaviour of a model compound (benzo(a)pyrene) under simulated aquatic conditions. The kinetics of sorption were comparable to those of other PAH compounds. The sorption equilibrium was extensively studied and found to be affected by several key parameters, notably sediment concentration. The sorption coefficient decreased substantially with the sediment concentration, from 9580 ml g(-1) at a sediment concentration of 0.067 g l(-1) to 1,110 ml g(-1) at a sediment concentration of 9.8 g l(-1). The results are consistent with previous reports and often explained by the presence of colloids. In this paper the dry weight concentration of colloids was determined and used for deriving the true sorption coefficient, which is up to an order of magnitude higher than the observed partition coefficient. The sorption of benzo(a)pyrene was also dependent on some of the particle properties, and the sorption coefficient was found to increase with the organic carbon content and specific surface area of sediment particles. The desorption of benzo(a)pyrene from sediment was shown to be relatively rapid, with implications for the potential remobilisation of benzo(a)pyrene and similar compounds.     

Survey of phthalate pollution in arable soils in China

The problem of pollution by phthalates is of global concern due to their widespread occurrence, toxicity and endocrine disruption properties. The contamination by phthalates such as dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) in 23 arable soils throughout China was investigated to evaluate the present pollution situation. The survey results demonstrated that phthalates were ubiquitous pollutants in soils in China. The total concentrations of phthalates differed from one location to another, and ranged from 0.89 to 10.03 mg kg(-1) with a median concentration of 3.43 mg kg(-1). Among the phthalates, DEHP was dominant and detected in all 23 soils. DEP and DBP were also in abundance, and DMP was rarely detected. Similar contamination patterns were observed in all 23 soils. A distinct feature of phthalate pollution in China was that the average concentration in northern China was higher than that in southern China. In addition, a close relationship was observed between the concentration of phthalates in soils and the consumption of agricultural film. The correlation showed that the application of agriculture film might be a significant pollution source of phthalates in arable soils of China. The potential risk of phthalates in soils was assessed on the basis of current guide values and limits.     

Distribution of PAEs in the middle and lower reaches of the Yellow River, China

Samples of water, sediment and suspended particulates were collected from 13 sites in the middle and lower reaches of the Yellow River in China. Phthalic acid esters (PAEs) concentrations in different phases of each sample were determined by Gas Chromatogram GC-FID. The results are shown as follows: (1) In the Xiao Langdi–Dongming Bridge section, PAEs concentrations in water phase from the main river ranged from 3.99 × 10⁻³ to 45.45 × 10⁻³ mg/L, which were similar to those from other rivers in the world. The PAEs levels in the tributaries of the Yellow River were much higher than those of the main river. (2) In the studied branches, the concentration of PAEs in sediment for Luoyang Petrochemical Channel (331.70 mg/Kg) was the highest. The concentrations of PAEs in sediment phase of the main river were 30.52 to 85.16 mg/Kg, which were much higher than those from other rivers in the world. In the main river, the concentration level of PAEs on suspended solid phases reached 94.22 mg/Kg, and it reached 691.23 mg/Kg in the Yiluo River – one tributary of the Yellow River. (3) Whether in the sediment or on the suspended solid phases, there was no significant correlation between the contents of PAEs and TOC or particle size of the solid phase; and the calculated Koc of Di (2-Ethylhexyl) Phthalate (DEHP) in the river were much less than the theoretical value, which inferred that PAEs were not on the equilibrium between water and suspended solid phases/sediment. (4) Among the measured PAEs compounds, the proportions of DEHP and di-n-butyl phthalate (DBP) were much higher than the others. The concentrations of DEHP exceeded the Quality Standard in all the main river and tributary stations except those in the Mengjin and Jiaogong Bridge of the main river. This indicates that more attention should be paid to pollution control and further assessment in understanding risks associated with human health.     

Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

重庆典型岩溶区地下河水体PAEs分布特征研究

分别采集了重庆典型岩溶区5条地下河水体10个样品,用气相色谱法对样品中的邻苯二甲酸酯类(PAEs)含量进行测定,分析其在重庆典型岩溶区地下河水体中的分布特征。结果表明,常见的19种邻苯二甲酸酯类(PAEs)在重庆典型岩溶区地下河水体中均有检出,其浓度范围为103.29~2268.78μg/L;5种被美国环保局列为优先控制的PAEs类污染物中,邻苯二甲酸二丁酯(DBP)和邻苯二甲酸双(2-乙基己基)酯是主要的污染物;与国内外其他地区水体进行比较,重庆典型岩溶区地下河水体PAEs含量处于较高污染水平。     

水体表面微层中DBP和DEHP的色谱测定

建立了用气相色谱（ＧＣ）和反相高效液相色谱（ＲＰＨＰＬＣ）分析邻苯二甲酸二丁酯（ＤＢＰ）和邻苯二甲酸二异辛酯（ＤＥＨＰ）的方法。首次在ＨＰＬＣ中用异丙醇作为流动相分离上述两种化合物,取得满意的结果。ＧＣ的检测限为ＤＢＰ２ｎｇ,ＤＥＨＰ２ｎｇ。ＨＰＬＣ的检测限为ＤＢＰ５ｎｇ,ＤＥＨＰ１０ｎｇ。两种方法都有良好的精密度、回收率,并用这两种分析方法分析了湖水水体表面微层水样中的ＤＢＰ和ＤＥＨＰ     

Phosphorus sorption–desorption behaviour of river bed sediments in the Abshineh river, Hamedan, Iran, related to their composition

Phosphorus (P) sorption by sediments may play a vital role in buffering P concentration in the overlying water column. To characterize P sorption–desorption in the river bed sediments, 17 bed sediment samples collected from Abshineh river, in a semi arid region, Hamedan, western Iran were studied through a batch experiment and related to sediment composition. The sorbed fraction ranged from 4.4% to 5.4% and from 38.5% to 86.0% of sorption maxima when 20 and 1,500 mg P kg^?1, respectively, was added to the sediment samples. Phosphorus sorption curves were well fitted to the Langmuir model. Zero equilibrium P concentration ranged from 0.10 to 0.51 mg P l^?1 and varied with sediment characteristics. Phosphorus desorption differed strongly among the studied bed sediments and ranged from 10.8% to 80.2% when 1,500 mg P kg^?1 was added. The results of the geochemical modelling indicated that even under low P addition (2 mg l^?1), the solutions are mainly saturated with respect to hydroxyapatite and ß-tricalcium phosphate minerals and undersaturated with respect to other Ca and Mg minerals, whereas under higher P addition (150 mg l^?1), most Ca–P solid phases, except the most soluble mineral (brushite), will likely precipitate. A Langmuir sorption maximum was positively correlated with carbonate calcium. Estimated P retention capacity of the bed sediments are generally lower and zero equilibrium P concentration values higher in upstream sites than at the downstream sites, suggesting that sediments in upstream and downstream may act as source and sink of P, respectively.     

鞍山市空气颗粒物中酞酸酯的季节变化与功能区差异

采用气相色谱-质谱仪(GC-MS)对辽宁省鞍山市空气颗粒物中15种酞酸酯夏季和冬季的浓度进行了分析测定,研究了酞酸酯污染水平的季节变化,不同功能区酞酸酯浓度的差异,以及DBP和DEHP在夏冬两季中的污染特点,将鞍山市夏冬两季酞酸酯的浓度与国内外部分城市进行了比较,分析了产生上述结果的原因,基本说明了鞍山市空气颗粒物中酞酸酯的污染状况。